Oil soluble dyes



' the reaction products of the esterified condensa- Pa'tented Jan. 1,1946; a

UNITED S ATES PATENT OFFICE a I 2,392,158 g No Drawing. ApplicationJanuary 9, 1943,

' Serial No. 471,916

10 Claims. (01.260-169) I v I This invention relates to dyestuflscontainthe dyes when reacted with these products coning acid groups, butsoluble or dispersible in 'stitute the preferred group in the presentinwater immiscible organic solvents. vention. j The large class ofdyestuflfs having acid groups 7 It is an' advantage of the presentinvention such as sulfonic and carboxylic groups have been 5 that theprocess of reactingthe esterifled con-' used extensively in the dyeingof basic nitrogdensation products with the dyes is not diflicult enousfibers and in the case of the direct dyes and that yie s are e ce e t. ima y c ses also for the dyeing oi cellulosic fibers. They are, ingsubstantially quantitative. In general the however, in general notsoluble or dispersible reaction is best it it takes place. betweeneither in water immiscible organic solvents such as 1 the free base andthe free acid dyestufl or the hydrocarbons, glyceride oils and the like,and, salt 01 the base with a strong acid such as hytherefore, this classor dyestuirs has not been drochloric d and t alkali metal salts of thegenerally used i fields which require th di dyestufl. Ineither casethereaction takes place persion or solution of the dyestuit in waterimreadily with moderate heating nd presents. 110 miscible solvents. l5 Prticular control roblems. Theproducts ob- According to the presentinvention, dye mfl tained are stable and are suitablelor variouscontaining acid groups are reacted with certain, s Such as process p int001011118 f P esterified condensation products of alkylene tics,888011116 a d e Transparent oxides or chlorhydrin and trialkylolamines.The P t are obtainable when. th are suitresulting products, which areprobablysalts or y p rsed in the medium. 1 v a similar compounds, aresoluble or dispersible in The present invention be illustrated in waterimmiscible solvents. The trialkylolamine ceniunction it t o wi specificexamples. is condensed with at least 5 equivalents of e Parts e y W ttalkylene oxide or chlorhydrin and the condensation product is esterifledwith a equivalents or v Example}: e an aliphatic acid having asufliciently long hy- 1 Parts: of methanohmmefire PM in drocarbon chain.The condensation products vessel fitted with, a brine-000131; refluxcorrespond to the formula: n e a se -led a itator and an. i lettuberhav- (cam) 0cm inga manifold with flne perforations under the 80surface of the triethanolamina, The charge is a 4 h h stirred rapidly,heated lQ0 11Q.C.,and 220 cm o ocn, parts of ethylene oxide arebubbledin through R1, R2, and R3 being residues of the same or the inlettube- Before introducing theethylene difier nt fatt acids. these mdicalsbeing am oxide a'trace of sodium orpotassium hydroxide hatic hydrocarbonradicals with at least eleven i added The P Q -X :arbon atoms, and :r,y, and 2 being integers Preferably mamtmned at a rate 80 h h their sumbeing at least eight. The present inmajor Pomon is abmrbedi' Any smallamount vention is applicable in general to all dyestuffs escaping iswndensed by 1111; condenser having acid groups, and since the productsare and returned Mn After soluble or dispersible in water immisciblesoll M theethylene onde P $b 13 t vents it broadens the field'ofusefulness for dyes m appears SPbStmmQ-DY P 9 3? d having these acidgroups. the Yield is P y q titative. I

The present invention is concerned only with d I w tion products withthedyes themselves and is 4 parts of triethanol hmine ai'eili dfih a,

not intended to cover the new esterifled convessel fitted with a c ldlfi' flux condensation products of alkylolamines and alkyldenser asealed a itator and anjinlet tube hav-j ene oxides, these forming thesubject matter of mg a manifold with fine, rforations under the ourcopending application, Serial No. 468,548, surface of thetriethanolamine.\ ,The'charge is filed December 10, 1942. While thenumber of stirred rapidly, heated to. 00-7 0.. and 440 alkylene oxidemolecules condensed with the parts of ethylene Oxi e arebu l in thr htrialkylolamine is not critical so long as there the inl u e- Bef reintroducing the ethylene are at least 5,'in general the products aremore oxide a trace of sodium or" potassium hydroxide satisfactory it thenumber of alkylene oxide is added.. The introductioniofethylene oxide isroups is at least 5 and not more than 15, and Preferably main a at a rae' -so f that the major portion is absorbed. Any small amount escapingis condensed by the reflux condenser and returned to the reactionmixture. After all of the ethylene oxide has been absorbed the mixtureappears substantially homogeneous and the yield is practicallyquantitative.

Example 3 149 parts of triethanolamine are placed in a vessel fittedwith a brine-cooled reflux condenser,asealedagitatorandaninlettubehavingamanifold with fine perforationsunderthe surface of the triethanolamine. The charge is stirred rapidly,heated to 100-110 C. and 660 parts of ethylene oxide are bubbled inthrough the inlet tube. Before introducing the ethylene oxide a trace ofsodium or potassium hydroxide is added. The introduction of ethyleneoxide is preferably maintained at a rate so that the major portion isabsorbed. Any small amount escaping is condensed by the reflux condenserand returned to the re-. action mixture. After all of the ethylene oxidehas been absorbed the mixture appears substantially homogeneous and theyield is practically quantitative.

. Example 4 yield is obtained. 40

Example 5 191 parts of tri-isopropanolamine are placed in a vesselfitted with a brine-cooled reflux condenser, a sealed agitator and aninlet tube having a manifold with fine perforationsunder the surface ofthe tri-isopropanolamine. The charge is rapidly stirred, heated to100-110 C. and 580 parts of propylene oxide are vaporized and the vaporsbubbled. in through the inlet tube. Before introducing the propyleneoxide a trace of sodium or potassium hydroxide is added to the reactionmixture. After all of the propylene oxide has been absorbed the mixturebecomes substantially homogeneous and an almost quantitative yield isobtained. 1

Example 6 149 parts of trlethanolamine are placed in a vessel fittedwith a brine-cooled reflux condenser, a sealed agitator and an inlettube having a manidenser, a sealed agitator and an inlet tube having amanifold with fine perforations under the surface of thetrl-isopropanolamine. The charge is rapidly stirred, heated to IOU-110c, and 220 parts of ethylene oxide are bubbled in through the inlettube. Before introducing the ethylene oxide a trace of sodium orpotassium hydroxide is added to the reaction mixture. After all of thefold with fine perforations under the surface of the triethanolamine.The charge is rapidly stirred, heated to -110 C. and 290 parts ofpropylene oxide are vaporized and the vapors bubbled in through theinlet tube. Before introducing the propylene oxide a trace of sodium orpotassium hydroxide is added to the reaction mixture. After all of thepropylene oxide has been absorbed the mixture becomes substantiallyhomo.

geneous and an almost quantitative yield is obtained.

Example 7 191 parts of-tri-isopropanolamine are placed in a vesselfitted with a brine-cooled reflux con- 75 t solvent naphtha, mixedhexanes, gaso-' ethylene oxide has been absorbed the mixture becomessubstantially homogeneous and an almost quantitative yield is obtained.

Example 8 The condensation product produced according to anyone of theseven preceding examples is heated with 3 moles of oleic acid in an openvat for a number of hours at -170 C. The heating is continued untilreaction is complete, which is substantially quantitative.

Example 9 The condensation product produced according to any one ofExamples 1-'! is heated with 3 moles of stearic acid in an open vat fora number of hours at bio- C. The heating is continued until reaction iscomplete, which i substantially quantitative.

Example 10 The condensation product produced according to any one ofExamples 1-7 is heated with 3 moles ofsoya bean acid in an open vat fora number of hours at 140-170? C. The heating is continued until reactionis complete, which is substan quantitative.

Example 11 The condensation product-produced according to any one ofexamples 1-7 is heated with 3 moles of lauric acid in an open vat for anumber of hours at 140-1'l0 C. The heating is continued until reactionis complete, which is substantially quantitative.

Example 12 Example 13 The product according to Example 1 is mixed with133 parts of 20 B. hydrochloric acid and esterifled with 888 parts ofoleic acid by heating at 1'70 C. until reaction is complete. Thehydrochloride of the ester is produced and is the same as obtained inthe preceding example.

In a'similar manner the products of Examples 2 and 3 may be esteriiiedin the presence of the corresponding amount of hydrochloric acid, usingeither oleic acid or any of the other acids described in Examples 5-7.

Example 14 A product according to Example 13 is placed in a reactionvessel provided with stirring and heating means and 0.3 molecularequivalent of Naphthol Green B (ferric complex CI 5) is slowly addedwith vigorous stirring and the reaction mixture is heated up to 70 C.andmaintained at this temperature until reaction is complete. The productis a green dye which is soluble in water immiscible organic solventssuch as benzene,

line, kerosene, lubricating oil, drying oils and the like.

Esamplefi I One mole of any of the esterifled products of Example 12 isplaced in a reaction vessel provided The procedure of Example 15 isfollowed but instead of the Patent Blue 0.5' mole of Direct Black E (CI581) is substituted. A black color is produced which is soluble in waterimmiscible organic solvents such as benzene, toluene, solvent naphtha,mixed hexanes, gasoline, kerosene, lubricating oil, drying oils and thelike.

Example 17 One mole of a free ester prepared according to any ofExamples 8-11 is heated at 70 C. with 0.9 mole of free acid of PatentBlue until reaction is complete. The product obtained is substantiallyidentical with that of Example 15.

Example 18- Example 19 One mole of any of the esterifled products ofExample 12 is placed in a reaction vessel provided with agitation andheating, and 0.6 mole of Nigrosine WS (01 865) is slowly added, assumingthat Nigrosine has a molecular weight of 400 and that the mixtureaverages 1.5 sulfonic acid groups per molecule of dye, the reactionmixture being heated with stirring to 70 C. and maintained at ,thistemperature until reaction is complete. The

product is a black which is soluble in water immiscible organic solventssuch as benzene, toluene, solvent naphtha, mixed hexanes, gasoline,kerosene, lubricating oil, drying oils and the like.

Example 20 One mole of any of the esterifled products of Example 12 isplaced in a reaction vessel provided with agitation and heating, and0.45 mole of Alizarine Cyanine Green (CI 1078) is slowly added, thereaction mixture being heated with stirring to 70 C. and maintained atthis temper-' ature until reaction is complete. The product is a greenwhich is soluble in water immiscible organic solvents such as benzene,toluene, solvent naphtha; mixed hexanes, gasoline, kerosene, lubricatingoil, drying oils and the like.

Other water-soluble dyestuffs containing acid groups in addition tothose in the above examples may also be converted'to organophillicdyestuffs by the same procedure. For example: an-

thraquinone acid dyes such as Alizarine Rubinol xG-C. I. 1091, AlizarineDirect Blue 3-0. I. 1087,

and Alizarine Sapphire Blue 13-6. 1054; thiazole dyestuffs such asDirect Fast Yellow 3-0. I. 814; nitro dyestuffs such as Naphthol Yellow8-0. I. 10: mono-azo dyestufis' such as Fast Light Orange 2G-C, I, 27,Croceine Orange- C. I. 26, Acid Brilliant Red, -RC. I. 32, Lake 'ScarletZR-C. I. 79, Bordeaux 3-0. I. 88, Fast Red A-C. I. 1'16,dis-azodyestuifs such as Naphthylamine Blue 3-0, I, 289; stilbenedyestuffs such as Stilbene Yellow 26-0. 1. 620 and Stilbene Orange R-C.I. 621; pyrazolone dyestufls such as Tartrazine--C. L 640;triphenylmethane dyestuffs such as Acid Light Green SF-C. I. 670,Soluble Blue R-C. I. 705, and Soluble Blue 3R- C. I. 706.

The presence of a large number of polar groups in the dye molecule suchas Allzarlne Sapphire Blue B, C. I. 1054, decreases the solubility ofthe resulting product in organic, water-immiscible solvents.

We claim: 1. A dyestufl dispersible in water immiscible organic solventscomprising the reaction product of a dyestufl having sulfonic acidgroups with an ester of a condensationproduct of ethylene oxide andtriethanolamine having the following formula:

chmo oea.

N(C:H4O),0CR:

(CaHsOhOCB! in which R1, R2 and R: are aliphatic hydrocarbon radicalshaving at least eleven carbon atoms, and a; w and z are integers andtheir sum is not less 2. A dyestufl dispersible in water immiscibleorganic solvents comprising the reaction product of a dyestuff havingsulfonic acid groups with an ester of a condensation product of ethyleneoxide and triethanolamine having the following formula:

(CsHrOhO CB1 (C:Ha0) 00 B1 (Ca to) .0 C RI m which R1, R2 and a; arealiphatic hydrocarbon (CIHAO)|OC|' II in which 2:, y and z are integersand their sum is not less than 8.

4. A dyestufi according to claim 3 in which the sum of :c, 11 and zequals 8. i

5. A dyestufi dispersible in water immiscible organic solventscomprising the reaction product Naphthol Green B with a triester of acondensation product having the following formula:

(CrH40)0 C Br N-(C:H40) '0 C RI (CrHrO) .0 C R: m which R1, R2 and R:are aliphatic hydrocarbon radicals of at least 11 carbon atoms, and z, 1and z are integers and their sum is not less than 8.

l c. A dyestufl according a, claim 5 in which the sum of :r. y and 2equals 8.

\ 7. A dyestufl dispersible in water immiscible organic solventscomprising the reaction product of Patent Blue A with a triester of acondensa- 5 a. A dyestuit dispersible m water immiscible organicsolvents comprising the reaction product of Direct Black E withatriesteroi a condensation product havi'ng thetollowing formula; 1 (cimonocm,

-(c,n.o).oca, (clnlohocn,

in which R1. R2 an a e a n c w o ar on. radicals of at least-ll carbonatoms, and y and, z are inte ers and their' m is o .le s-;th=n. 1

10. 11 dycstuii! according 32 claim g in which the sum of :c, y-and 2equals 8. v

mmamn n

